Regeni, IreneChowdhury, RituparnoTerlinden, KaiHoriuchi, ShinnosukeHolstein, Julian J.Feldmann, SaschaClever, Guido H.2024-11-212024-11-212023-07-17http://hdl.handle.net/2003/42800http://dx.doi.org/10.17877/DE290R-24633A strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non-statistical metallosupramolecular self-assembly is introduced. For this, the DPP backbone is equipped with nitrogen-based donors that allow for different discrete assemblies to be formed upon the addition of Pd(II), distinguished by the number of π-stacked chromophores. A Pd3L6 three-ring, a heteroleptic Pd2L2L′2 ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self-penetrated motifs (a Pd2L3 triple and a Pd2L4 quadruple stack), were obtained and systematically investigated. With increasing counts of stacked chromophores, UV/Vis absorptions red-shift and emission intensities decrease, except for compound Pd2L2L′2, which stands out with an exceptional photoluminescence quantum yield of 51 %. This is extraordinary for open-shell metal containing assemblies and explainable by an intra-assembly FRET process. The modular design and synthesis of soluble multi-chromophore building blocks offers the potential for the preparation of nanodevices and materials with applications in sensing, photo-redox catalysis and optics.enChromophoresCoordination cagesEnergy transferSelf-assemblySupramolecular chemistry540Text